Sprayable hair treatment composition

ABSTRACT

A hairspray composition is described that includes a nonionic polymer and an anionic polymer. The nonionic polymer is formed from monomers having at least one unneutralized carboxylic acid. The anionic polymer is identical to the nonionic one, except that all of the carboxylic acid groups are in salt form. Advantageously, the composition further includes an acrylic resin, most especially an amphoteric one. Best results are achieved when the acrylic resin is neutralized with a relatively small cation such as potassium and a second cation of a water soluble fatty amine. These compositions employ water as the carrier and dimethyl ether as propellant.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to hairspray compositions, especially thoseformulated to meet VOC emission standards.

2. The Related Art

Chemically based consumer products have come under ever increasingenvironmental scrutiny. Spray formulations have been particularlyimpacted by environmental concerns. Legislation has been enacted to banchlorofluorocarbons as propellants in aerosol spray compositions.Successor propellants in the form of volatile hydrocarbons have alsocome under scrutiny. Not only propellants but even solvents such asethanol are undergoing restriction.

California's legislation concerning volatile organic compounds (VOC) hasforced future hairspray products to replace, at least in part, theorganic solvent with water. Concentrations of organic propellantspresent in water-based solvents must also be adjusted to relatively lowlevels. With such constraints, certain problems have arisen.Water-dispersed systems are slow to dry. Not only do they result inwetness on the hair but there is also an undesirable initial curldroopage due to water being placed on the curl. Quite significantlythere is also difficulty in developing the style. Resins formulated in awater-based system can have weak holding power.

A body of literature has developed that attempts to meet theseenvironmental related challenges. Replacement of chlorofluorocarbonswith hydrocarbon propellants has been discussed in U.S. Pat. No.4,859,455 (Nowak, Jr. et al.). Improved tolerance to the hydrocarbonlevels was reported as being achieved through neutralization of acrylicresins with mixtures of sodium or potassium hydroxide and certain longchain amines. U.S. Pat. No. 5,021,238 (Martino et al.) reports thefurther advance of using dimethyl ether (DME) as a hairspray propellant.DME allows use of water as the only solvent thereby significantlyreducing the volatiles problem.

Recently there has been disclosed in U.S. Pat. No. 5,068,099 (Sramek) anaerosol hairspray package claiming reduced volatile organic compoundemission during the useful life of the package. The spray compositioncontains a combination of at least two polymers differing in weightaverage molecular weight by at least 1.5. This blend of polymerscombines with a low delivery rate discharge mechanism to provide anatomized composition with mean particle size of at least 60 microns. Asignificant drawback of this technology is the necessity for verysubstantial amounts of volatile alcohol; water is present at levels nohigher than 10% by weight. Instead of eliminating volatiles from theformula, the patent merely controls the spray emission thereof.Unfortunately, at some point in the life cycle of the package, volatileswill be emitted into the atmosphere.

Even though there have been significant advances in this art, manyproblems still remain. Some systems are excellent at reducing volatileorganic compounds but hair hold, wetness and other physical propertiesare not equivalent to the old volatile solvent-based formulas. In otherinstances, physical properties are excellent but there is eitherinsufficient volatiles reduction or the systems are too costly.

Accordingly, it is an object of the present invention to provide ahairspray composition that reduces volatile organic compound emissionsto the atmosphere thereby being environmentally friendly.

Another object of the present invention is to provide a hairspraycomposition which is a water-based system.

A further object of the present invention is to provide a hairspraycomposition for a water-based system that has improved holding andstyling characteristics.

A still further object of the present invention is to provide ahairspray composition for a water-based system that dries fairly quicklyand does not impart any undue wet or cool feel to hair or scalp.

These and other objects of the present invention will become moreevident from the following summary and detailed description.

SUMMARY OF THE INVENTION

An aqueous hairspray composition is provided including:

(i) a nonionic film-forming polymer constituted from at least onemonomer having at least one unneutralized carboxylic acid group; and

(ii) an anionic film-forming polymer which is the nonionic film-formingpolymer all of whose carboxylic acid groups have been converted to asalt form;

the relative weight ratio of nonionic to anionic film-forming polymerranging from about 10:1 to about 1:10.

Compositions of this invention can further include an acrylic resinconstituted from at least one monomer having at least one carboxylicgroup, all of the carboxylic groups being in salt form. Advantageously,the acrylic resin is a water-soluble amphoteric polymer with carboxylicgroups neutralized with an appropriate neutralizing agent. This resin ispreferably randomly neutralized with a water soluble C₈ -C₂₂ fatty amineand an alkali metal base, ammonia, a C₁ -C₆ alkanolamine or a C₁ -C₆alkyl amine.

In a further aspect of the invention, the composition includes a C₂ -C₄alkylene carbonate to plasticize the polymers and to help better wetsurfaces of the hair.

Hairspray compositions of this invention are dispersed in water whichmay contain from 0-50% of a propellant such as dimethyl ether.

DETAILED DESCRIPTION

It has been discovered that many of the objects of the present inventioncan be achieved through a composition that includes a nonionic waterinsoluble film-forming polymer having at least one monomer with at leastone unneutralized carboxylic acid group in conjunction with an anionicfilm-forming polymer, of identical structure to the nonionic polymerexcept that all the carboxylic acid groups are neutralized with aneutralizing agent into a salt form. In water, the anionic polymer willbe present as a solubilized resin while the nonionic polymer will bepresent as an insoluble resin dispersion. Three functions are served bythe anionic polymer. Firstly, the anionic plasticizes the nonionicpolymer. Secondly, the anionic polymer coats hair to improvewettability. Thirdly, the whole system is stabilized by the anionicpolymer so that the product does not cream.

The nonionic insoluble polymer dispersion serves several functions.Firstly, it releases water from the drying film faster than the anionicsolution, allowing faster drying. Secondly, it increases the overallsolids content without building viscosity or destroying the sprayabilityof the overall system. By contrast, soluble high molecular weightanionics in sufficient quantitities will not allow proper atomization ofthe system even though the solution viscosity may be low. This limitsthe concentration of the anionic polymer species as high concentrationswill decrease sprayability.

The nonionic film-forming polymer must be constituted of at least onepolymer having at least one unneutralized carboxylic acid group as partof its structure. Typical monomers include those selected from the groupconsisting of acrylic acid, methacrylic acid, crotonic acid, fumaricacid, maleic acid, itaconic acid and combinations thereof. Amounts ofthe monomer with the at least one carboxylic acid group will be presentfrom about 1 to about 80%, preferably from about 3 to about 50%,optimally from about 5 to about 30% by weight of the total nonionicpolymer. Comonomers forming the nonionic polymer may be selected fromthe group consisting of α-methylstyrene, styrene, divinylbenzene, vinylacetate, vinyl neodecanoate, acrylamide, methacrylamide, C₁ -C₂₀ estersof acrylic or methacrylic acids, C₁ -C₂₀ esters of maleic or fumaricacids and combinations thereof. Amounts of the hydrophobic comonomerswill range from about 20 to 99%, preferably from about 50 to 97%,optimally from about 70 to about 85% by weight. Preferred nonionicpolymers include: methacrylic acid/methyl methacrylate/ethyl acrylate;methacrylic acid/styrene/butylacrylate; methacrylic acid/methylmethacrylate/butyl acrylate; acrylic acid/vinylacetate/butyl acrylate.Most preferred is 5-15% methacrylic acid/30-40% methylmethacrylate/50-60% ethyl acrylate, available from

Amounts of the nonionic polymer will range from about 0.5 to about 10%,preferably from about 1 to about 8%, optimally from about 2 to about 6%by weight.

A second essential element of compositions according to the presentinvention is an anionic film-forming polymer. The antionic polymer willbe identical to the nonionic polymer, except that all of the carboxylicacid groups will be neutralized into salt form. Typical cations formingthe salt as counterions to the carboxylate groups are those selectedfrom the group consisting of alkalimetal, alkaline earth metal,ammonium, C₁ -C₆ alkanolammonium, C₁ -C₂₂ alkyl ammonium cations andcombinations thereof. Examples of suitable neutralizing agents that formthe aforementioned cations include sodium hydroxide, potassiumhydroxide, 2-amino-2- methyl-1,3-propanediol (AMPD);2-amino-2-ethyl-1,3-propanediol (AEPD); 2-amino-2-methyl-1-propanol(AMP); 2-amino-1-butanol (AB); monoethanolamine (MEA); diethanolamine(DEA); triethanolamine (TEA); monoisopropanolamine (MIPA);diisopropanolamine (DIPA); and triisopropanolamine (TRIPA).

Amounts of the anionic polymer will range from about 0.5 to about 10%,preferably from about 1 to about 8%, optimally from about 1.5 to about4% by weight.

Best performance of compositions according to the present invention isachieved with the additional presence of an acrylic film-forming resinconstituted from at least one monomer with at least one carboxylicgroup, all of the at least one carboxylic groups being in salt form.Preferably the acrylic resin is amphoteric. Illustrative of monomerswith the at least one carboxylic group are acrylic acid and saltsthereof, methacrylic acid and salts thereof, maleic acid and saltsthereof, fumaric acid and salts thereof, crotonic acid and salts thereofand mixtures of these monomers. Amounts of the aforementioned monomersmay range from about 1 to about 99% by weight. Illustrative comonomersthat will contribute positive charge to form the amphoteric structureare C₁ -C₈ alkyl aminomethacrylate, C₁ -C₈ alkylaminoacrylate andmixtures thereof. Typical comonomers are t-butylaminoethyl methacrylate,t-butylaminopropyl acrylate, N,N-diethylaminoethyl acrylate,N,N-dimethylaminoethyl methacrylate and combinations thereof. Amounts ofthe comonomer will range from about 1 to about 30%, preferably fromabout 5 to about 20% by weight of the acrylate polymer. Most preferredis a resin copolymer of octyl acrylamide/acrylates/butylaminoethylmethacrylate, available under the trademark Amphomer® from the NationalStarch and Chemical Corporation, Bridgewater, N.J.

A particularly preferred embodiment of the acrylic resin is where thecarboxylic groups are randomly neutralized to a salt form having acation selected from the group consisting of ammonium, alkalimetal (suchas potassium or sodium), C₁ -C₆ alkanolammonium and C₁ -C₆ alkylammoniumcations. In conjunction therewith the resin is also randomly neutralizedwith a water soluble C₈ -C₂₂ fatty ammonium cation derived from arespective amine neutralizing agent. Relative weight amounts of thefirst and second acrylic neutralizing agents will range from about 10:1to 1:10, preferably from about 5:1 to 1:5, optimally between about 2:1and 1:2. Most preferred is a combination of Amphomer® resin neutralizedwith potassium hydroxide in combination with a second neutralizing agentof a water soluble PEG-5 cocoamine such as Ethomeen C15®.

The acrylic resin functions to plasticize both the nonionic and anionicpolymers but will stop short of solubilizing them, solubilizationpreventing the sprayability of the polymers. This resin also functionsto improve washability of the overall system. Optimum plasticization isachieved by the combination of different neutralization counterions andthe ratios of the long chain amine to short chain amine or inorganicalkali base neutralizing agent.

Amounts of the acrylic resin within compositions of this invention mayrange from about 0.5 to about 10%, preferably from about 1 to about 5%,optimally between about 1.5% and 3% by weight.

Relative weight ratios of nonionic to anionic polymer will range fromabout 10:1 to about 1:10, preferably from about 5:1 to about 1:5,optimally from about 3:1 to 1:2. The relative weight ratio of nonionicand anionic polymer combined to that of the acrylic resin, when present,will range from about 30:1 to about 1:2, preferably from about 15:1 toabout 5:1, optimally about 10:1.

Compositions of the present invention will also include water as acarrier for the polymers and other components. Water will be present inamounts ranging from about 20% to about 99%, preferably from about 40%to about 95% by weight. Optimally, water will be the major if notexclusive liquid carrier for the hair treatment compositions of thisinvention. Volatile organic solvents such as methanol, ethanol orisopropanol are preferably absent, but may be present to aid drying orreduction of vapor pressure of the propellant.

The present hair treatment compositions may be formulated as sprays inaerosol or nonaerosol forms. If an aerosol hairspray is desired, apropellant must be included in the composition. This agent isresponsible for expelling the other materials from the container andforming the hairspray character.

The propellant gas will be a C₁ -C₆ alkyl ether, most preferablydimethyl ether. Amounts of the ether will range from about 10 to about45%, preferably from about 30 to about 40%, optimally between about 32and 37% by weight.

Small quantities of surfactant ranging anywhere from about 0.1 to about10%, preferably from about 0.1 to about 1%, optimally about 0.3% byweight, may be present in the compositions of the invention. Thesurfactant may be an anionic, nonionic or cationic emulsifier.Particularly preferred are nonionic emulsifiers which are formed fromalkoxylation of hydrophobes such as fatty alcohols, fatty acids andphenols. Illustrative of such material is Triton X-100, and isoctylphenyl polyethoxyethanol. Fluorinated surfactants such as Zonyl®available from DuPont are particularly preferred and can be used inconjunction with the other surfactants.

Another useful component of compositions according to the presentinvention is that of a C₂ -C₄ alkylene carbonate present in an amountfrom about 0.05 to 1.0%, preferably from about 0.1 to 0.8%, optimallybetween about 0.2 and 0.5% by weight. Most preferred is propylenecarbonate. This material functions as a co-plasticizer and also helps tobetter wet the surface of hair.

Another useful plasticizer is Lubrigel® available from the Dash Company.This material is a combination of glycerin and methacrylic acid. Amountsmay range from about 0.1 to 2% by weight.

Compositions of this invention may contain any other ingredient normallyused in hairsprays. These other ingredients may include antifoam agents,proteins, antioxidants, fragrances, antimicrobials and sunscreens. Eachof these ingredients will be present in an amount effective toaccomplish its purpose.

Hairspray formulations of the present invention may, if desired, bepackaged in a pump spray container operated without any propellant.Otherwise, the composition may be charged into a suitable pressurizablecontainer which is sealed and then charged with propellant according toconventional techniques.

The following examples will more fully illustrate the embodiments ofthis invention. All parts, percentages and proportions referred toherein and in the appended claims are by weight unless otherwiseindicated.

EXAMPLE 1

A pair of hairspray compositions corresponding to the present inventionare displayed in Tables I and II. Performance tests of these hairspraysagainst a typical commercial alcohol/hydrocarbon propellant productindicated at least as good hold and wetness control properties. Theresults were surprising in view of the considerable water present in thetest formula.

                  TABLE I                                                         ______________________________________                                        COMPONENT               WEIGHT %                                              ______________________________________                                        Phase A                                                                       Amphomer LV 71 ®    2.380                                                 Potassium Hydroxide (87%)                                                                             0.292                                                 Deionized Water         26.279                                                Ethomeen C15 ®      0.474                                                 Phase B                                                                       Methacrylic Acid/Methyl methacrylate/                                                                 18.960                                                Ethyl acrylate (25% dispersion)                                               Lubrigel ®          0.790                                                 Propylene Carbonate     0.395                                                 Zonyl FSP ®         0.200                                                 Fragrance               0.105                                                 Triton X-100 ®      0.100                                                 Antifoam                0.025                                                 Phase C                                                                       Methacrylic Acid/Methyl methacrylate/                                                                 13.000                                                Ethylacrylate (15% solution potassium                                         hydroxide neutralized)                                                        Propellant                                                                    Dimethyl Ether          37.000                                                ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        COMPONENT               WEIGHT %                                              ______________________________________                                        Phase A                                                                       Deionized Water         37.490                                                Potassium Hydroxide (87%)                                                                             0.300                                                 Methacrylic Acid/Methyl 6.240                                                 methacrylate/Ethyl acrylate (25%                                              dispersion)                                                                   Phase B                                                                       Amphomer 4910 ®     1.900                                                 Ethomeen C15 ®      0.310                                                 Phase C                                                                       Lubrigel ®          0.630                                                 Propylene Carbonate     0.630                                                 Zonyl FSP ®         0.100                                                 Triton X-100 ®      0.100                                                 Antifoam                0.025                                                 Phase D                                                                       Methacrylic Acid/Methyl 15.170                                                methacrylate/Ethylacrylate (20%                                               dispersion)                                                                   Phase E                                                                       Dimethyl Ether          37.000                                                ______________________________________                                    

EXAMPLE 2

A series of hairspray compositions were formulated to evaluate theeffect of relative weight ratio of nonionic to anionic film-formingpolymer. Compositions of these hairsprays and their performance arelisted under Table III.

                                      TABLE III                                   __________________________________________________________________________                               SAMPLE (WT. %)                                                                A       B     C     D                              __________________________________________________________________________    Phase A                                                                       Amphomer LV 71 ®       2.380   2.380 2.380 2.380                          Potassium Hydroxide (87%)  0.292   0.292 0.292 0.292                          Deionized Water            29.809  26.279                                                                              22.546                                                                              15.119                         Ethomeen C15 ®         0.474   0.474 0.474 0.474                          Phase B                                                                       Triton X-100 ®         0.100   0.100 0.100 0.100                          Lubrigel ®             0.790   0.790 0.790 0.790                          Propylene Carbonate        0.355   0.355 0.355 0.355                          Fragrance                  0.105   0.105 0.105 0.105                          Dow Corning ® Antifoam 0.025   0.025 0.025 0.025                          Phase C                                                                       Methacrylic Acid/Methylmethacrylate/Ethyl Acrylate                                                       24.400  18.860                                                                              13.400                                                                              2.400                          (25% dispersion                                                               Phase D                                                                       Methacrylic Acid/Methylacrylate/Ethyl Acrylate (15%                                                      4.070   13.000                                                                              22.333                                                                              40.660                         solution potassium hydroxide neutralized to pH 9.05)                          Phase E                                                                       Dimethyl Ether             37.000  37.000                                                                              37.000                                                                              37.000                         Ratio of Nonionic to Anionic Polymer                                                                     10:1    2.4:1 1:1   1:10                           Physical Properties                                                           Viscosity (cps)            9       19.5  24    30                             pH                         7.07    7.26  7.8   8.44                           Performance                                                                   Sprayability               excellent                                                                             excellent                                                                           excellent                                                                           poor                           Rinsability                poor    excellent                                                                           excellent                                                                           excellent                      Appearance (when sprayed on hair)                                                                        white droplets                                                                        semi-clear                                                                          semi-clear                                                                          clear droplets of                                         of poor droplets of                                                                         droplets of                                                                         good wettability                                          wettability                                                                           good  good  Foams-Very                                                        wettability                                                                         wettability                                                                         large droplets                 Hair Hold                  poor    excellent                                                                           excellent                                                                           unacceptable                                                      (stiff)                                                                             (stiff)                                                                             (due to poor                                                                  spray)                         Film Properties            somewhat                                                                              excellent                                                                           excellent                                                                           excellent                                                 brittle (flexible)                                                                          (flexible)                                                                          (flexible)                     __________________________________________________________________________

When the ratio of nonionic to anionic polymer is 10:1, as in Sample A,the hairspray has excellent sprayability but is borderline rinseable andthe film is somewhat brittle. On the reverse ratio Sample D,sprayability is only borderline but rinseability and film properties areexcellent. Optimum performance is seen for Samples B and C withrespective ratios of 2.4:1 and 1:1. Sprayability, rinseability and filmproperties of B and C are all excellent.

EXAMPLE 3

Another series of hairspray compositions were prepared to evaluatevarious criticalities of the present invention.

The formula of Sample E is listed below.

    ______________________________________                                        SAMPLE E                                                                      COMPONENTS           WEIGHT %                                                 ______________________________________                                        Methacrylic Acid/Methyl                                                                            37.000                                                   Methacrylate/Ethyl Acrylate (25%                                              dispersion)                                                                   Deionized Water      25.000                                                   Fragrance            0.1200                                                   Dimethyl Ether       37.000                                                   ______________________________________                                    

The pH of this hairspray was 6.90 and viscosity was 3.5 cps. Thishairspray was placed in an aerosol can and sprayed onto hair swatches.Sprayability was excellent with the spray easily being broken up intofine particles. However, when sprayed onto the hair swatch, the presenceof white droplets were observed which did not wet out well onto the hairshafts. A subjective evaluation determined that there was poor hold andstiffness when compared to a standard commercial spray such as Rave® No.3. Rinseability was poor with large white flakes left on the hair. Filmproperties were also poor, being brittle and powdery with noflexibility. The conclusion drawn from this experiment is that anonionic polymer in dispersion form, in the absence of any anionicpolymer, is unsuitable as a hairspray.

The formula of Sample F is listed below.

    ______________________________________                                        SAMPLE F                                                                      COMPONENTS            WEIGHT %                                                ______________________________________                                        Methacrylic           60.000                                                  Acid/Methylmethacrylate/Ethyl Acrylate                                        (25% dispersion)                                                              Potassium Hydroxide (50% solution)                                                                  1.700                                                   Deionized Water       38.000                                                  ______________________________________                                    

The above composition was neutralized to pH 9.47 and formed a clearsolution of polymer with minimal Tyndall effect. Viscosity of thesolution was 17 cps. This composition was then formulated into a pair ofaerosol hairspray products with the finished products being the formulaslisted below.

                  TABLE IV                                                        ______________________________________                                                      FORMULA F FORMULA F'                                                          (Weight %)                                                                              (Weight %)                                            ______________________________________                                        Methacrylic     37.80       32.00                                             Acid/Methylmethacrylate/                                                      Ethyl                                                                         Acrylate                                                                      Potassium Hydroxide (50%                                                                      1.07        0.905                                             Solution)                                                                     Deionized Water 24.13       30.095                                            Dimethyl Ether  37.00       37.00                                             % Solids        9.45        8.0                                               ______________________________________                                    

Sample F was unsprayable. It streamed and foamed upon exit from thespray nozzle. Sample F' was better but still not acceptable.

These samples were sprayed onto hair swatches despite the very poorspray quality, the materials wetted well the hair shafts with clearliquid. Subjective evaluation indicated excellent hold that appearedequivalent to Rave® No. 3. Film properties were good. A continuous filmformed of good flexibility. Rinseability was also very good. The resinswashed out of the hair swatches very well leaving no residuals.

Based on the foregoing results, we conclude that a totally neutralizedpolymer system such as the anionic film-forming polymer alone would notbe suitable for use as a hairspray at higher resin levels due to poorsprayability. However, neutralization did improve rinseability, filmproperties, hold and wetting out of solution onto the hair shaft.

In the following experiment the resins utilized for samples E and F werecombined into one system. The formulation is listed below.

    ______________________________________                                        SAMPLE G                                                                      COMPONENTS              WEIGHT %                                              ______________________________________                                        Methacrylic             20.000                                                Acid/Methylmethacrylate/Ethyl Acrylate                                        (25% Dispersion)                                                              Methacrylic             33.000                                                Acid/Methylmethacrylate/Ethyl Acrylate                                        (15% Solids Neutralized with Potassium                                        Hydroxide to pH 9.45)                                                         Deionized Water         17.000                                                Dimethyl Ether          37.000                                                ______________________________________                                    

Total resin solids was 10%. The pH of the hairspray was 7.08 withviscosity of 4 cps.

Excellent sprayability was achieved with the desired fine breakup ofparticles. Upon wetting out onto the hair shafts, there was littleevidence of white droplets as seen with the unneutralized dispersion.

Sample G was comparable to Rave® No. 3 in stiffness. However, bondsbroke easily with flexing and rinseability was not quite acceptable.There were some definite deposits left on the hair in the form offlakes. Film properties were more brittle than the neutralized sampleand performance was not comparable to Rave® No. 3 (control).

From this we conclude the combination of the dispersion (nonionic) andneutralized (anionic) polymers can provide a high solids sprayablesystem. However, film properties, rinseability and hold would not bequite sufficient for commercial purposes.

In the following experiment, Sample G was repeated in a single stepprocess to eliminate use of two separate blending tanks. The formula ofSample H is listed below.

    ______________________________________                                        SAMPLE H                                                                      COMPONENTS              WEIGHT %                                              ______________________________________                                        Methacrylic             40.000                                                Acid/Methylmethacrylate/Ethyl Acrylate                                        (25% Dispersion)                                                              Potassium Hydroxide (87% Pellets)                                                                     0.587                                                 Deionized Water         22.413                                                Dimethyl Ether          37.000                                                ______________________________________                                    

The procedure here involved dissolving potassium hydroxide into water towhich was added the polymer dispersion while mixing until homogeneous.The resulting concentrate had a pH of 7.95 with viscosity of 310 cps.

The formula was filled into an aerosol can. The resulting product wasnot sprayable, demonstrating streaming and foaming upon ejection fromthe aerosol can.

In the following example, Sample I, the single step process was againutilized but the polymer was added in such a manner that only half ofthe dispersion was completely neutralized and the other half completelyunneutralized (as in Sample G).

    ______________________________________                                        SAMPLE I                                                                      COMPONENTS              WEIGHT %                                              ______________________________________                                        Methacrylic             40.000                                                Acid/Methylmethacrylate/Ethyl Acrylate                                        (25% Dispersion)                                                              Potassium Hydroxide (87% Pellets)                                                                     0.587                                                 Deionized Water         22.413                                                Dimethyl Ether          37.000                                                ______________________________________                                    

Formation of the concentrate was achieved by dissolving potassiumhydroxide in water and then adding half of the polymer dispersion whilemixing. Upon obtaining a uniform solution, the remaining half of thepolymer dispersion was added. By this procedure, all of the first halfof the polymer dispersion had its carboxylate groups neutralized whilenone of the second half polymer dispersion was neutralized. Thisprocedure avoided a random neutralization of the total polymerdispersion.

At the completion of the addition of the first half of the polymerdispersion, the concentrate was a clear solution which then revertedback into a milky dispersion upon addition of the second half of thepolymer. The pH of the resulting sample was 7.90 with viscosity of 28cps.

The sample was filled into an aerosol. Good sprayability and break-up ofparticles was observed.

Results from this sample demonstrated that for optimum performance it isnecessary to have the polymer dispersion in two distinct forms. One formmust be completely neutralized and the other form completelyunneutralized. Random neutralization of all the polymer dispersion as inExample H results in a non-sprayable concentrate.

The foregoing description and Examples illustrate selected embodimentsof the present invention. In light thereof, various modifications willbe suggested to one skilled in the art, all of which are within thespirit and purview of this invention.

What is claimed is:
 1. An aqueous hairspray composition comprising:(i) a nonionic film-forming polymer constituted from at least one monomer having at least one unneutralized carboxylic acid group wherein said nonionic polymer is a copolymer of methacrylic acid/methyl methacrylate/ethyl acrylate; (ii) an anionic film-forming polymer which is identical to the nonionic film-forming polymer except that all of carboxylic acid groups have been converted to a salt form; and (iii) about 10 to about 45% dimethyl ether as a propellant;the relative weight ratio of nonionic to anionic film-forming polymer ranging from about 10:1 to about 1:10.
 2. A composition according to claim 1 further comprising from about 0.5 to about 10% of an amphoteric acrylic film forming resin constituted from at least one monomer having at least one carboxylic group, all of the carboxylic groups being in salt form.
 3. A composition according to claim 2 wherein the amphoteric resin is a copolymer of octyl acrylamide/acrylates/butylaminoethyl methacrylate.
 4. A composition according to claim 2 wherein the total weight ratio of nonionic and anionic polymers combined to acrylic resin ranges from about 30:1 to about 1:2.
 5. A composition according to claim 4 wherein the total weight ratio ranges from about 15:1 to about 5:1.
 6. A composition according to claim 1 wherein the salt form of the anionic polymer comprises a cation selected from the group consisting of ammonium, alkalimetal, alkaline earth metal, C₁ -C₂₂ alkyl ammonium, C₁ -C₆ alkanolammonium and cation combinations thereof.
 7. A composition according to claim 3 wherein the acrylic resin is randomly neutralized to a pair of salt forms, a first of the salt forms having a cation selected from the group consisting of ammonium, alkalimetal, alkaline earth metal, C₁ -C₆ alkylammonium and C₁ -C₆ alkanolammonium cations, and a second of the salt forms having a cation which is a water soluble C₈ -C₂₂ fatty ammonium cation, the relative weight ratio of first to second salt forms ranging from about 5:1 to about 1:5.
 8. A composition according to claim 1 wherein the dimethyl ether is present in an amount from about 30 to about 37% and is the sole propellant. 